EP0546814B1 - A polyimide photosensitive cover coating agent - Google Patents
A polyimide photosensitive cover coating agent Download PDFInfo
- Publication number
- EP0546814B1 EP0546814B1 EP92311220A EP92311220A EP0546814B1 EP 0546814 B1 EP0546814 B1 EP 0546814B1 EP 92311220 A EP92311220 A EP 92311220A EP 92311220 A EP92311220 A EP 92311220A EP 0546814 B1 EP0546814 B1 EP 0546814B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- compound
- coating agent
- groups
- cover coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 0 *CC1CCCC1 Chemical compound *CC1CCCC1 0.000 description 3
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
Definitions
- This invention relates to a photosensitive cover coating agent used for coating flexible circuit bases. More particularly, it relates to a photosensitive cover coating agent which is easily produced and superior in compatibility, sensitivity, heat resistance, flexibility, adhesion and electrical properties.
- the insulating protective coating for printed wiring board has been required for the insulating protective coating for printed wiring board to satisfy any characteristics of heat resistance sufficiently endurable to solder immersion, firm adhesion onto circuit base and electrical insulating properties, and in the case of flexible printed wiring board, it has been further required to satisfy flexibility in addition to the above-mentioned characteristics.
- cover lay film has been used as insulating protective film for printed wiring board.
- an adhesive is coated onto one side surface of polyimide or polyester film, followed by boring only a terminal-connecting part by means of punching or the like, positioning the part onto a circuit base by hand operation and adhering the film at a high temperature and under a high pressure by means of hot plate pressing.
- the resulting film is superior in the flexibility and advantageous in the aspect of circuit protection, but a problem has been raised.
- CAD design language
- the cost of mold preparation by means of CAD and the plant cost for hot plate processing become high.
- the positioning onto the wiring board becomes difficult.
- an adhesive is applied, smears are liable to occur at the time of boring process by means of drill or the like and there is a fear that the adhesive exudes out at the time of pressing.
- cover lay ink On the other hand, a process of forming an insulating protective film on the printed wiring board according to a printing method (cover lay ink) has been developed.
- a cover lay inking agent having been presently used is the one having applied a solder resist, so far used for rigid base; hence there has been a problem that the agent is inferior in the flexibility and insufficient in the heat resistance, electrical properties and adhesion onto the base.
- the reactivity of the resin is rapid, it has very often been used in a two-part form; hence its handling is cumbersome, and the pot life after mixing of the two parts is so short that a problem of storage stability has been raised.
- Japanese patent application laid-open No. Sho 55-145717 discloses a composition consisting of an epoxy acrylate resin and a melamine resin, but the composition has a disadvantage of poor flexibility.
- Japanese patent publication Nos. Sho 50-4395 and Sho 53-10636 disclose acrylic resin compositions of sulfomethylene acrylate, phosphoric acid ethylene acrylate, etc., but while any of them are relatively good in the flexibility, they are notably inferior in the heat resistance.
- the pattern dimension is limited due to positioning of the cover lay film on the wiring board, exudation of adhesive at the time of pressing, etc.
- the pattern dimension has a limitation of 100 ⁇ m, due to the positioning on the wiring board, exudation, sagging, etc. of the pattern. Such a limitation cannot correspond to pattern fining of circuit base to be required in future.
- a fining process by means of a lithography process using a photosensitive material is a technique capable of sufficiently corresponding to pattern fining of circuit base.
- the photosensitive material includes highly heat-resistant, photosenstive polyimides. Most of these polyimides are a material obtained by introducing a photosensitive group into a polyimide precursor or a polyimide or a material obtained by mixing a compound having a photosensitive group with a polyimide precursor.
- Japanese patent publication No. Sho 55-41422 proposes a process for preparing the polyimide by imparting a photosensitive group to the side chain of a polyamic ester
- Japanese patent laid-open No. Sho 60-6729 proposes a process for preparing the polyimide by preparing a diamine having a double bond in advance, followed by preparing the polyimide using the diamine.
- the process of introducing the functional group is complicated and a high cost is required.
- Japanese patent application laid-open Nos. Sho 55-45746 and Sho 60-100143 each propose a process of reacting an unsaturated epoxy compound or a double bond-containing isocyanate compound with the carboxyl group of a polyamic acid, but the process has a drawback that when the unsaturated group-containing compound is reacted with the carboxyl group of the polyamic acid, a portion of the polyamic acid decomposes to lower the solution viscosity.
- Japanese patent application laid-open Nos. Sho 63-206741, Sho 59-15449 and Hei 2-144539 propose a composition obtained by mixing a polyamic acid with a photoreactive, unsaturated group-containing compound, but since such unsaturated group-containing compounds are usually inferior in the compatibility with polyamic acid, practically the use conditions and the kinds of the unsaturated group-containing compound or polyamic acid are restricted; hence the above compounds are diffcultly used.
- a photosensitive cover coating agent consisting of a polyamic acid mentioned below, a specified polyfunctional monomer and a photopolymerization initiator or a sensitizing agent is superior in the compatibility, sensitivity, heat resistance, adhesion, electrical properties and flexibility.
- the object of the present invention is to provide a photosensitive cover coating agent forming an insulating protective coating superior in the compatibility, sensitivity, heat resistance, adhesion, electrical properties and flexibility.
- the present invention consists in
- the polyamic acid used in the photosensitive cover coating agent of the present invention is obtained by reacting an organic tetracarboxylic dianhydride with an organic diamine, and the reaction is usually carried out in an organic solvent.
- the reaction of obtaining the polyamic acid is an exothermic reaction, and it is preferable to control the reaction under cooling, if necessary. Further, there is also preferable a process of suspending or dissolving either one of a tetracarboxylic anhydride and a diamine in an organic solvent, followed by reacting while adding the other, and even if either one of the two components is used in an excess quantity within a range of 10:9 to 9:10, there is no problem.
- the tetracarboxylic dianhydride is expressed by the formula (III) wherein R 1 represents and used alone or in a combination of two kinds or more thereof.
- diamines such as 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-di(m-aminophenoxy)diphenyl sulfone, 4,4'-di(p-aminophenoxy)diphenyl sulfone, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-2,2-propane, 1,5-diaminonaphthalene
- aromatic diamines such as 4,4'-diaminodiphen
- Examples of the solvent used for the reaction of the tetracarboxylic dianhydride with the diamine to form the polyamic acid are N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N-methylcaprolactam, dimethyl sulfoxide, hexamethylphosphoamide, tetramethylenesulfone, tetramethylurea, ⁇ -butyrolactone, N-acetyl-2-pyrrolidone, phenol, cresols, nitro compounds, chlorine solvents such as chloroform, methylene chloride, etc., cellosolves (Cellosolve is a Trade Mark), carbitols, etc.
- a general-purpose solvent such as benzene, toluene, xylene, etc. may be added to the above solvents.
- an aminosilane expressed by the formula H2N-R 5 -SiR 6 (3-k)Yk wherein R 5 represents -(CH 2)s -, -(CH 2 ) s -(phenylene group)-(CH 2 ) s -o-(phenylene group)- or -(phenylene group)-wherein s represents an integer of 1 to 4, R 6 independently represents an alkyl group of 1 to 6 carbon atoms, phenyl group or an alkyl-substituted phenyl group of 7 to 12 carbon atoms, Y independently represents a hydrolyzable alkoxy group, an acetoxy group or a halogen atom and k has a value of 1 ⁇ k ⁇ 3.
- aminosilane examples are the following known compounds, but it is not always limited these examples:
- the viscosity of the resulting polymer it is preferred to adjust the viscosity to a viscosity of 500 to 100,000 mPa ⁇ s, preferably 5,000 to 50,000 mPa ⁇ s as measured by E type viscometer (Rotar 3°xR14).
- the other parts than acryloyl groups or methacryloyl groups are not particularly limited, and compounds having various structures may be used. Most of them are easily obtained as commercially available products.
- the preferable number of acryloyl groups or methacryloyl groups is 4 or less, more preferably 2, in one molecule.
- Z in the formula (II) is an aliphatic group or an alicyclic group and the number of carbon atoms is preferably 1 to 10.
- R 3 is a hydrogen atom or an aliphatic group, an alicyclic group, an aromatic group or an araliphatic group of 1 to 10 carbon atoms which may be substituted with one or more of unsaturated bonds or hydroxyl, carboxyl, ether, amide, ester or ketone group.
- the group R 3 is preferably hydrogen or a hydroxyl, carboxyl amide or nitrile group.
- R 4 is a hydrogen atom or -Z-R 3 .
- R 4 is a hydrogen atom, a product having a higher sensitivity is obtained; hence R 4 is preferably a hydrogen atom.
- Examples of the compound (C) expressed by the formula (II) are the following amino compounds, but it is not limited to the examples: H 2 N-CH 2 CH 2 CH 3 ,H 2 N-CH 2 CH 2 CH 2 CH 3 , H 2 N-CH 2 CH 2 CH 2 CH 2 CH 3 H 2 N-CH 2 -OH, H 2 N-CH 2 CH 2 -OH H 2 N-CH 2 CH 2 CH 2 CH 2 -OH, H 2 N-CH 2 CH 2 OCH 2 CH 2 -OH H 2 N ⁇ CH 2 CH 2 CH 2 CH 2 ⁇ COOH
- the quantity of the compound (C) added is 0.01 to 0.80 molar equivalent based upon the compound (B). If it is less than 0.01 molar equivalent, the compatibility of the polyamic acid with the compound having acryloyl groups or methacryloyl groups is inferior and the sensitivity is low. If it exceeds 0.80 molar equivalent, the developing properties, the sensitivity and the stability of the photosensitive cover coating agent with lapse of time become inferior. Further, the total quantity of the compound (B) and the compound (C) is 20 to 200 parts by weight based upon 100 parts by weight of the polymer (A). If the quantity is less than 20 parts by weight, the sensitibity is low, while if it exceeds 200 parts by weight, the quality of the polyimide film as the final product becomes inferior.
- the compound having acryloyl groups or methacryloyl groups and the amino compound are mixed in the polyamic acid solution, or they are mixed in a solvent or without any solvent in advance, followed by adding to and mixing with tne polyamic acid solution. At that time, heat generation often occurs; thus, in order to prevent decomposition of the polyamic acid and thermal polymerization of the compound having acryloyl groups or methacryloyl groups, cooling down to 70°C or lower is preferred.
- the photopolymerization initiator or sensitizer (D) the following compounds may be used alone or in admixture: benzophenone, Michler's ketone, 4,4'-diethylaminobenzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzyl, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propane, 3,3'
- the quantity of the photopolymerization initiator or sensitizer added is 0.05 to 20 parts by weight based upon 100 parts by weight of the polymer. If it is less than 0.05 part by weight, its effect is poor, while if it exceeds 20 parts by weight, the film quality becomes inferior. Its preferable quantity added is 0.5 to 10 parts by weight.
- Examples of such a compound are as follows: butyl acrylate, cyclohexyl acrylate, dimethylamino-ethyl methacrylate, benzyl acrylate, carbitol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, N-methylolacrylamide, diacetone acrylamide, N-vinylpyrrolidone, etc.
- a bisazido compound such as 2,6-bis(p-azidobenzylidene)-cyclohexanone, 2,6-bis(p-azidobenzylidene)-4-methylcyclohexanone, 2,6-bis(p-azidobenzylidene)-4-tert-butylcyclohexane, etc. to 100 parts by weight of the polymer (A).
- the photosensitive cover coating agent of the present invention is obtained.
- the photosensitive cover coating agent of the present invention is usually applied in the form of a solution.
- the solution is coated onto the total surface of the printed circuit base according to a known method such as roll coating method, doctor knife method, comma coater method, spray coating method, screen printing method, etc., followed by baking the resulting material in an oven to remove most of the solvent in the coating.
- a negative mask is put on the coating, followed by irradiation with X-rays, electronic rays, ultraviolet rays, visible rays, etc., and ultraviolet rays are particularly preferable.
- an aqueous solution of NaOH, KOH, Na 2 CO 3 , tetramethylammonium hydroxide, trimethylhydroxyethyl ammonium hydroxide or the like is usable, and if necessary, an alcohol, a surfactant or the like is further added to the above.
- the finally obtained pattern is baked at 200° to 250°C to afford the objective insulating protective coating of a printed wiring board having superior heat resistance, flexibility, adhesion, electrical properties, etc.
- a 2 l capacity, four-neck, separable flask provided with a stirrer, a thermometer and a nitrogen gas-purging means was fixed on a water bath.
- To this flask was added dehydrated and purified N-methyl-2-pyrrolidone (600 ml) in a nitrogen gas current. Further, to the flask was added 4,4'-diaminodiphenyl ether (60.46 g, 302.0 mmol), followed by suspending and dissolving together.
- pyromellitic dianhydride 65.87 g, 302.0 mmol
- the thus obtained polyamic acid solution had a viscosity of 39,000 mPa ⁇ s as measured under conditions of a solids concentration of 17% by weight and an E type viscometer: rotor 3°xR14, 20 rev/min (hereinafter this viscometer being employed).
- the thus obtained polyamic acid solution had a solids concentration of 16% by weight and a viscosity of 12,000 mPa ⁇ s as measured by the E type viscometer.
- the thus obtained polyamic acid solution had a solids concentration of 15% by weight and a viscosity of 25,000 mPa ⁇ s as measured by the E type viscometer.
- the thus obtained polyamic acid solution had a solids concentration of 20% by weight and a viscosity of 9,000 mPa ⁇ s as measured by the E type viscometer.
- the thus obtained polyamic acid solution had a solids concentration of 15% by weight and a viscosity of 50,000 mPa ⁇ s as measured by the E type viscometer.
- Polyethylene glycol 400 diacrylate (PEG-400DA, trade name of product made by Nihon Kayaku Co., Ltd.) (100 g) and ethanolamine (4.0 g) were mixed with stirring at 30°C, for one hour.
- the polyamic acid solution (100 g) obtained in Reference example 1 the mixed solution (17 g) obtained above, Michler's ketone (0.85 g) and 2,4-diethylthioxanthone (Kayacure-DETX, trademark of product made by Nihon Kayaku Co., Ltd.) (0.85 g), were mixed with stirring and dissolving them together, to obtain the photosensitive cover coating agent of the present invention.
- the thus obtained solution was coated onto a flexible copper-lined sheet (a polyimide base of 30 ⁇ m thick) by means of Baker's applicator, followed by heat-treating the resulting sheet in an oven at 100°C for 10 minutes and then subjecting the heat-treated sheet to exposure to ultraviolet light by means of a mercury lamp, vacuum, both surfaces-exposing machine (MPL-S, trade name of product made by Print Denshi Sogyo Co., Ltd.) fitted with a high pressure mercury lamp (HL-10201 BF, trade name of product made by Ushio Denki Co., Ltd.), through a test photomask.
- MPL-S both surfaces-exposing machine
- HL-10201 BF high pressure mercury lamp
- the resulting material was developed with a 5% Na 2 CO 3 aqueous solution for one minute, followed by rinsing it with purified water for one minute, drying in an oven at 100°C for 10 minutes, further elevating the temperature up to 240°C to carry out heat treatment for 30 minutes.
- the resulting coating was subjected to measurements of coating thickness before the development, developing properties, sensitivity, heat resistance, flexibility, adhesion and electrical properties. The results are shown in Table 1.
- the conductor pattern of the flexible copper-lined sheet (polyimide base thickness: 60 ⁇ m) having no coating a conductor pattern having formed a conductor in one reciprocation of a conductor width of 1.5 mm and a clearance of 1.0 mm, by etching, was used.
- a conductor pattern of the flexible copper-lined sheet having a coating a conductor pattern having formed a cover coating film on the conductor pattern of the flexible copper-lined sheet having no coating was used.
- the heat resistance when the coating was floated on a solder bath at 280°C for 60 seconds, the peeling, buldge and discoloration of the coating were judged by naked eyes, and a coating having no change observed between before and after the test was regarded as good, while a coating having any change observed was regarded as inferior.
- the adhesion was evaluated based upon JIS K 5400 and according to the judgement standards of Japan Paint Engineering Association (Foundation). Namely, a section of 1 cm square was divided by lines each having an interval of 1 mm longitudinally and laterally, and only the coating was cut by means of a cutter knife so as to give 100 sections of 1 mm square along these lines and nicks were provided so that the base could not be cut. Next, a cellophane tape was applied onto the nicked coating, followed by pulling up the tape at an angle of 90°, and evaluating the adhesion by counting what number of the sections of 1 mm square were peeled off at that time. A coating without any peeling and any deficit in the respective sections was regarded as good, while a coating having one or more peelings and having a deficit was regarded as inferior.
- EO-modified bisphenol F diacrylate (Kayarad R-712, trademark of product made by Nihon Kayaku Co., Ltd.) (12.95 g) and n-butylamine (0.65 g) were added to the polyamic acid solution (100 g) obtained in Reference example 1, followed by mixing them with stirring at 30°C for 2 hours, further adding Michler's ketone (0.31 g) and 2,2-dimethoxy-2-phenylacetophenone (1.53 g) and mixing them and dissolving together to obtain a photosensitive cover coating agent of the present invention.
- Oligo ester diacrylate (M-6100, trade name of product made by Toa Gosei Kagaku Kogyo Co., Ltd.) (100 g) and ethanolamine (4.0 g) were mixed with stirring at 30°C for one hour.
- the polyamic acid solution (100 g) obtained in Reference example 2 the above-mentioned mixed solution (16 g), 3,3',4,4'-tetra(t-butylperoxycarbonylbenzophenone(BTTB, trade name of product made by Nihon Yushi Co., Ltd.) (0.8 g) and 2,4-diethylthioxanthone (Kayacure-DETX, trademark of product made by Nihon Kayaku Co., Ltd.) (0.80 g) were mixed, agitated and dissolved together to obtain a photosensitive cover coating agent of the present invention.
- BTTB 3,3',4,4'-tetra(t-butylperoxycarbonylbenzophenone
- BTTB
- Neopentyl glycol-modified trimethylolpropane diacrylate (R-604, trade name of product made by Nihon Kayaku Co., Ltd.) (80 g), pentaerythritol triacrylate (made by Kokusan Kagakusha Co., Ltd.) (20 g) and ethanolamine (5 g) were mixed with stirring at 30°C for one hour.
- the polyamic acid solution (100 g) obtained in Reference example 3 the above-mentioned mixed solution (15 g), isopropylthioxanthone (Quantacure-ITX, trademark of product made by Ward Blenkinsop Co., Ltd.) (0.60 g) and 2-methyl-1-[4-methylthio)phenyl]-2-morpholino-1-propane (Irgacure-907, trademark of product made by Ciba Geigy Co., Ltd.) (0.60 g) were mixed, agitated and dissolved together to obtain a photosensitive cover coating agent of the present invention.
- isopropylthioxanthone Quantacure-ITX, trademark of product made by Ward Blenkinsop Co., Ltd.
- 2-methyl-1-[4-methylthio)phenyl]-2-morpholino-1-propane Irgacure-907, trademark of product made by Ciba Geigy Co., Ltd.
- Polyethylene glycol 400 diacrylate (PEG-400DA, trade name of product made by Nihon Kayaku Co., Ltd.) (9.43 g), oligo ester diacrylate (M-6100, trade name of product made by Toa Gosei Kagaku Co., Ltd.) (9.43 g) and 1-amino-2-propanol (1.14 g) were added to the polyamic acid solution (100 g) obtained in Reference example 4, followed by mixing them with stirring at 30°C for 2 hours and further adding, mixing and dissolving together Michler's ketone (1.0 g) and 2,4-diethylthioxanthone (1.0 g) to obtain a photosensitive cover coating agent of the present invention.
- PEG-400DA trade name of product made by Nihon Kayaku Co., Ltd.
- M-6100 trade name of product made by Toa Gosei Kagaku Co., Ltd.
- Polyethylene glycol 400 diacrylate (PEG-400DA, trade name of product made by Nihon Kayaku Co., Ltd.) (100 g) and ethanolamine (4.0 g) were mixed with stirring at 30°C for one hour.
- the polyamic acid solution (100 g) obtained in Reference example 5 the above-mentioned mixed solution (15 g), Michler's ketone (0.75 g) and 2,4-diethylthioxanthone (Kayacure-DETX, trademark of product made by Nihon Kayaku Co., Ltd.) (0.75 g) were mixed, agitated and dissolved together to obtain a photosensitive cover coating agent.
- Example 1 Measurements were carried out as in Example 1. As a result, the developing properties were inferior and there was a residual coating at the unexposed part.
- EO-modified bisphenol F diacrylate (Kayarad R-712, trademark of product made by Nihon Kayaku Co., Ltd.) (16.0 g),Michler'sketone(0.8 g) and2,2-dimethoxy-2-phenylacetophenone (0.8 g) were added to the polyamic acid solution (100 g) obtained in Reference example 2, followed by mixing them and dissolving together to obtain a photosensitive cover coating agent.
- Dimethylaminoethyl methacrylate (13.50 g), Michler's ketone (0.76 g) and 2,4-diethylxanthone (kayacure-DETX, trademark of product made by Nihon Kayaku Co., Ltd.) (0.76 g) were mixed with the polyamic acid solution (100 g) obtained in Reference example 1, followed by agitating the mixture and dissolving together to obtain a photosensitive cover coating agent.
- the photosensitive cover coating agent of the present invention can be easily prepared using cheap materials, and is superior in the compatibility of the materials with one other, sensitivity, heat resistance, flexibility, adhesion and electrical properties; hence it is very useful as an insulating protective coating for flexible circuit bases.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Paints Or Removers (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP350325/91 | 1991-12-09 | ||
JP03350325A JP3084585B2 (ja) | 1991-12-09 | 1991-12-09 | ポリイミド系感光性カバーコート剤 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0546814A1 EP0546814A1 (en) | 1993-06-16 |
EP0546814B1 true EP0546814B1 (en) | 1997-09-17 |
Family
ID=18409719
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92311220A Expired - Lifetime EP0546814B1 (en) | 1991-12-09 | 1992-12-09 | A polyimide photosensitive cover coating agent |
Country Status (4)
Country | Link |
---|---|
US (1) | US5326792A (ja) |
EP (1) | EP0546814B1 (ja) |
JP (1) | JP3084585B2 (ja) |
DE (1) | DE69222276T2 (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5851736A (en) * | 1991-03-05 | 1998-12-22 | Nitto Denko Corporation | Heat-resistant photoresist composition, photosensitive substrate, and process for forming heat-resistant positive or negative pattern |
JP3687988B2 (ja) * | 1993-09-03 | 2005-08-24 | 日立化成工業株式会社 | i線ステッパ用感光性樹脂組成物 |
JPH08220792A (ja) * | 1995-02-10 | 1996-08-30 | Toyo Ink Mfg Co Ltd | 光分解性電子写真用トナー |
US6071667A (en) * | 1995-04-13 | 2000-06-06 | Hitachi Chemical Co., Ltd. | Photosensitive resin composition containing a photosensitive polyamide resin |
KR100529577B1 (ko) | 2001-11-22 | 2005-11-17 | 미쓰이 가가쿠 가부시키가이샤 | 감광성 수지조성물, 드라이필름 및 그것을 이용한 가공부품 |
US7220490B2 (en) * | 2003-12-30 | 2007-05-22 | E. I. Du Pont De Nemours And Company | Polyimide based adhesive compositions useful in flexible circuit applications, and compositions and methods relating thereto |
US7524617B2 (en) * | 2004-11-23 | 2009-04-28 | E.I. Du Pont De Nemours And Company | Low-temperature curable photosensitive compositions |
CN101675387B (zh) * | 2007-04-24 | 2012-10-10 | 三井化学株式会社 | 感光性树脂组合物、干膜以及使用该干膜的加工品 |
CN101663617B (zh) * | 2007-04-24 | 2013-05-08 | 三井化学株式会社 | 感光性树脂组合物、干膜及使用它的加工品 |
JP6754098B2 (ja) * | 2015-01-30 | 2020-09-09 | 日産化学株式会社 | カーボネート骨格を有する加水分解性シランを含むリソグラフィー用レジスト下層膜形成組成物 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1127340A (en) * | 1977-12-30 | 1982-07-06 | Kohtaro Nagasawa | Photocurable light-sensitive composition and material |
JPS5843449A (ja) * | 1981-09-09 | 1983-03-14 | Hitachi Ltd | 感光性重合体組成物 |
JPS5962661A (ja) * | 1982-09-30 | 1984-04-10 | Nitto Electric Ind Co Ltd | 感光性樹脂組成物 |
US4629685A (en) * | 1984-11-16 | 1986-12-16 | Ciba-Geigy Corporation | Process for irradiating polyimides |
JPS627762A (ja) * | 1985-07-05 | 1987-01-14 | Hitachi Ltd | 感光性重合体組成物 |
JP2949813B2 (ja) * | 1989-09-19 | 1999-09-20 | 東レ株式会社 | 化学線感応性重合体組成物 |
-
1991
- 1991-12-09 JP JP03350325A patent/JP3084585B2/ja not_active Expired - Lifetime
-
1992
- 1992-11-23 US US07/980,164 patent/US5326792A/en not_active Expired - Lifetime
- 1992-12-09 DE DE69222276T patent/DE69222276T2/de not_active Expired - Fee Related
- 1992-12-09 EP EP92311220A patent/EP0546814B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP3084585B2 (ja) | 2000-09-04 |
JPH05158237A (ja) | 1993-06-25 |
US5326792A (en) | 1994-07-05 |
EP0546814A1 (en) | 1993-06-16 |
DE69222276D1 (de) | 1997-10-23 |
DE69222276T2 (de) | 1998-02-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3721768B2 (ja) | 感光性ポリイミドシロキサン組成物および絶縁膜 | |
JP4199294B2 (ja) | 感光性樹脂組成物及びこれを用いた回路基板 | |
EP1219662B1 (en) | Polyamic acid ester | |
EP0601203B1 (en) | Photosensitive resin composition | |
JP2011017898A (ja) | 感光性カバーレイ | |
EP0546814B1 (en) | A polyimide photosensitive cover coating agent | |
US6143475A (en) | Polyimide precursor, polyimide and their use | |
JP2826940B2 (ja) | i線露光用感光性組成物 | |
US5587275A (en) | Photosensitive resin composition and a process for forming a patterned polyimide film using the same | |
KR0161542B1 (ko) | 감광성 수지 조성물 | |
JP4592999B2 (ja) | 新規な末端修飾したポリアミック酸及びそれを含む感光性樹脂組成物 | |
US6096480A (en) | Photosensitive polyimidosiloxane compositions and insulating films made thereof | |
JP4183459B2 (ja) | ポリアミド酸エステル組成物 | |
JP2010256881A (ja) | 感光性樹脂組成物 | |
US5616448A (en) | Photosensitive resin composition and a process for forming a patterned polyimide film using the same | |
JPH0850354A (ja) | i線用感光性組成物 | |
JPH11223946A (ja) | 感光性樹脂組成物、これを用いた感光性ソルダーレジストの製造法 | |
JP4772493B2 (ja) | シロキサン含有ポリアミック酸樹脂組成物及びフィルム材料並びに回路基板の製造方法 | |
JP2000039710A (ja) | 感光性樹脂組成物及びレリーフパターンの製造法 | |
EP0755962A2 (en) | Photosensitive polyimidosiloxanes and compositions and insulating films made thereof | |
JPH0836264A (ja) | i線露光用組成物 | |
JP2001125273A (ja) | プラズマエッチングレジスト及びエッチング法 | |
JP2993128B2 (ja) | 感光性樹脂組成物の製造法 | |
JPH05216224A (ja) | 感光性樹脂組成物 | |
JP3040866B2 (ja) | 感光性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
17P | Request for examination filed |
Effective date: 19930802 |
|
17Q | First examination report despatched |
Effective date: 19960118 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB |
|
REF | Corresponds to: |
Ref document number: 69222276 Country of ref document: DE Date of ref document: 19971023 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19981112 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19991123 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19991209 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19991209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011002 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: TP |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20111219 Year of fee payment: 20 |